DE3628082A1 - CARBOXAMIDES, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE FOR CONTROLLING Pests - Google Patents

Abstract

Carboxamides of the general formula I <IMAGE> (I) where R1 is C1-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, C3-C10-cycloalkyl, C3-C10-cycloalkyenyl or C4-C10-cycloalkenylalkyl, and R2 and R3 are each hydrogen, halogen, C1-C3-alkyl, C1-C3-alkoxy, C1-C3-haloalkyl. C1-C3-haloalkoxy or methylthio, and their use for combating pests.

Description

The invention relates to new carboxamides of the formula I.

in the
R ^{1 is} alkyl, alkenyl or alkynyl each having up to 6 carbon atoms or cycloalkyl or cycloalkenyl each having up to 10 carbon atoms,
R ² , R ^{3 are the} same or different and represent hydrogen, halogen, alkyl or alkoxy each having up to 3 carbon atoms or methylthio and
X means oxygen, sulfur, methylene or sulfoxi.

The compounds of formula I are very good insecticidal and acaricidal active and known active ingredients of similar structure or the same Consider direction of action.

As active ingredients with a similar structure viewed the substances described in DE-OS 26 33 069.

Unlike most pesticides known to date, that kill, paralyze or drive away the animals as contact or feeding poisons, the compounds of formula I engage in the hormonal system of animal organism. In the case of insects, for example, the conversion to Imago, the storage of viable eggs and the development disturbed by normal eggs and thereby the sequence of generations interrupted. The agents according to the invention are practical for vertebrates non-toxic. The compounds of formula I moreover easily become substances degraded that occur in the natural environment and from microorganisms be further disassembled. The danger of accumulation is therefore locked out. They can therefore be used to combat harmlessly Pests used in animals, plants and supplies and in water will.  

The carboxamides of the formula I can be reacted accordingly 2-phenoxy-ethylamines with corresponding acid halides can be obtained:

Hal is preferably a chlorine atom for economic reasons.

The 2-phenoxyethylamines required for the preparation of the compounds I. are z. B. known from European patent application 4,334 or leave produce themselves according to the synthetic method described there. The acid halides also required are known and for the most part customary.

An acid binder is usually required for the reaction; one either uses an excess of the 2-phenoxyethylamine itself or the usual basic agents, especially aliphatic, aromatic and heterocyclic amines, e.g. B. triethylamine, dimethylamine, piperidine, Dimethylaniline, dimethylbenzylamine, pyridine and 4-dimethylaminopyridine.

The reaction is conveniently carried out in a solution or Running diluent. The following are suitable, for example: aliphatic and aromatic, optionally chlorinated Hydrocarbons, such as petroleum ether, benzene, toluene, xylene, gasoline, Dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloromethane, Chlorobenzene, ether or esters such as diethyl and di-n-butyl ether, Methyl tert-butyl ether, tetrahydrofuran, dioxane, ethyl acetate; Ketones, for example acetone, methyl ethyl ketone, methyl isopropyl ketone; also nitriles, such as acetonitrile and propionitrile, aprotic dipolar Solvents such as dimethylformamide, dimethyl sulfoxide or pyridine. Also Mixtures of these substances can act as solvents or diluents be used.  

Usually, the starting materials are used in a stoichiometric ratio a. However, an excess of one or the other can occur in individual cases be quite beneficial.

The reaction usually proceeds above -30 ° C with sufficient Speed. 100 ° C must i. a. not be exceeded. Since they're in In some cases where heat is generated, it can be an advantage be to provide a cooling facility.

The compounds of formula I according to the invention can also according to practically all known methods of carboxamide synthesis are, for example by reacting 2-phenoxyethylamines with corresponding carboxylic acid esters, carboxylic acids or their salts, Carboxylic anhydrides or ketene derivatives (cf. C. Ferri, reactions of Organic synthesis, Georg Thieme Verlag, Stuttgart 1978, p. 542 and the literature cited there).

The reaction mixture is worked up in a conventional manner, for. B. by Mix with water, separate the phases and column chromatography.

Some of the new compounds of formula I fall in the form of colorless ones or slightly brownish-colored, viscous oils, which are characterized by prolonged use Warm to a moderately elevated temperature under reduced pressure ("Andestillieren") free from the last volatile components and open let it clean this way. Obtaining the compounds of formula I in crystalline form, it can be purified by recrystallization respectively.

Carboxamides in which R ^{1 is} cyclopropyl or alkenyl, R ² or R ^{3 is} hydrogen or fluorine and X are oxygen, with the following combinations being particularly advantageous: R ¹ = cyclopropyl or alkenyl and R ² and R ³ = Hydrogen.

In the following, IR spectra with typical absorption maxima from the so-called "fingerprint" range between 1500 cm ^-1 and 900 cm ^-1 are used to characterize the new carboxamides of the formula I. The compounds listed without physical information can be obtained in a corresponding manner and used as active ingredients.

example 1

10.1 g of 2- (4-phenoxy-phenoxy) ethylamine are anhydrous in 40 ml Pyridine dissolved. With the help of an ice bath, the mixture is cooled to 5 ° C. with stirring from. A solution of 2,2-dimethylbutyric acid chloride is then left slowly add dropwise in 20 ml of methylene chloride. After finishing strong exothermic reaction is stirred for 12 hours at 25 ° C, in triplicate Poured volume of water and extracted four times with methylene chloride. The extract is washed thoroughly with water, over sodium sulfate dried and i. V. restricted. You take in the backlog Hexane / methyl tert-butyl ether (4: 1) and filtered through silica gel -60 (Merck). After the solvent has been stripped off, a solid remains can be recrystallized from hexane / methyl tert-butyl ether. Beige crystals, mp: 47-48 ° C. Yield: 8.8 g, 61% of arithmetically possible amount.

C ₂₀ H ₂₅ NO ₃ (327)

calc .: C 73.4 H 7.7 N 4.3 Found: C 73.3 H 7.6 N 4.2

Infrared absorptions (cm ^-1 ): 1487, 1465, 1232, 819.

Example 2

8.01 g of 2- (4-phenoxy-phenoxy) ethylamine are dissolved in 50 ml of ethyl acetate, and 5.6 g of pyridine are added. While cooling with ice, 3.65 g of cyclopropanecarboxylic acid chloride in 25 ml of ethyl acetate are added dropwise. After the heat has subsided, the mixture is stirred for a further 10 hours at room temperature and filtered. The clear solution is washed three times with water, 5% hydrochloric acid and again with water, dried over sodium sulfate and concentrated in a rotary evaporator. It is recrystallized from petroleum ether / ethyl acetate (3: 1), 5.4 g of an almost colorless crystal powder having a melting range of 101 to 102 ° C.
Yield: 52% of the calculated amount.

C ₁₈ H ₁₉ NO ₃ (297)

calc .: C 72.7 H 6.4 N 4.7 found: C 72.5 H 6.4 N 4.7

Infrared absorptions (cm ^-1 ) 1491, 1252, 1228, 1037, 841

The compounds listed in the table below were also obtained in the ways described in Examples 1 and 2, as far as they are identified by their absorption spectra; other Compounds corresponding to formula (I) can be used in the same way with appropriate modification of the regulations according to the required amount and (because of the best reaction conditions) may be obtained after the preliminary test.

table

To demonstrate the superior effect of the substances according to the invention now the active ingredient from Example 2 with a corresponding, good effective compound from DE-OS 26 33 069 compared:

Example 2

Comparison according to DE-OS 26 33 069

Dysdercus breeding trial (Dysdercus intermedius)

1 l mason jars are filled with 200 g sterile quartz sand, the with 25 ml the aqueous active ingredient preparation is mixed. Be in every jar 20 larvae set in the 4th larval stage, with swollen cotton seeds to be fed.

At the time of adult moulting in the control group, it is rated whether typical juvenoid effects appear, namely shortened or curved Wing. Such individuals are sterile and short-lived.

Aedes breeding trial (Aedes aegypti)

250 ml plastic cups are filled with 200 ml tap water. About 20 larvae of Aedes aegypti (L3-L4) are used, the aqueous Preparation of the solution is added. The larvae are until Pupation or fed to hatch; the slip of the Mosquitos.

Breeding attempt (Prodenia litura)

Raube (L3) are placed on nutrient medium, which is one before cooling aqueous active ingredient preparation was added. Typical are rated Juvenoid effects, namely the red coloring of the caterpillars, the disturbed construction of one Doll cradle and the missing pupation. Each approach consists of 5 animals.

Claims (6)

1. Carboxamide of the formula I. in the
R ^{1 is} alkyl, alkenyl or alkynyl each having up to 6 carbon atoms or cycloalkyl or cycloalkenyl each having up to 10 carbon atoms,
R ² , R ^{3 are the} same or different and represent hydrogen, halogen, alkyl or alkoxy each having up to 3 carbon atoms or methylthio and
X means oxygen, sulfur, methylene or sulfoxi. 2. A process for the preparation of carboxamides of the formula I according to claim 1, characterized in that a corresponding 2-phenoxyethylamine II with an appropriate acid halide III implements. 3. pesticide containing a carboxamide according to Claim 1.   4. Pesticides containing a solid or liquid Carrier and at least one carboxamide of the formula I according to Claim 1. 5. Use of carboxamides of the formula I according to claim 1 for Pest control. 6. A method for controlling pests, characterized in that an effective amount of the carboxamide according to claim 1 Pests or their habitat.